Porous polymer network materials

Abstract

Functionalized Porous Polymer Networks (PPNs) exhibiting favourable characteristics such as high surface area′ and gas uptake properties are disclosed, including methods of making such networks. A method of preparing a porous polymer network, comprising: (a) a step of homo-coupling a monomer in the presence of 2,2′-bipyridyl, 1,5-cycloocta-1,5-diene, a mixed solvent of DMF/THF and a compound or mixture selected from the group consisting of bis(1,5-cydoocta-1,5-diene)nickel(0), Ni(PPH3) 4, and Zn/NiCI2/NaBr/PPH3 at a temperature in the range of 20 to 40° C. These stable PPNs may be useful in the context of carbon capture, gas storage and separation, and as supports for catalysts.

The invention claimed is: 
     
       1. A porous polymer network comprising a moiety of Formula (A) 
       
         
           
           
               
               
           
         
         wherein T is —C, —Si, —Ge, —Sn, —P,—B, —N, —C 10 H 16 , —NO 2 , —CHO, —OH, —OCH 3  or —OCH 2 CH 3 , 
         R 1  to R 16  are each independently selected from —H, —F, —Cl, —Br, —I, —OH, —NH 2 , an alkyl, CH 2 Q, COQ and SO 2 Q, wherein Q is a functional group, with the proviso that when at least one of R 1  to R 16  is CH 2 Q, Q is not an alkyl group, and wherein at least one of R 1  to R 16  is CH 2 -polyamine. 
       
     
     
       2. The porous polymer network according to  claim 1 , wherein T is selected from the group consisting of —C, —Si, —Ge and —C 10 H 16 . 
     
     
       3. The porous polymer network according to  claim 1 , wherein T is —C or —Si. 
     
     
       4. The porous polymer network according to  claim 1 , wherein the functional group is selected from an alkyl group having 1 to 6 carbon atoms, an amine and a polyamine. 
     
     
       5. The porous polymer network according to  claim 1 , wherein the functional group is selected from —C 3 H 7 , —C 4 H 9 , —C 5 H 11  and —C 6 H 13 . 
     
     
       6. The porous polymer network according to  claim 1 , wherein the polyamine is represented by N(A 1 )A 2 , wherein A 1  and A 2  are each independently selected from —H, a saturated or unsaturated polyalkylamine and a saturated or unsaturated polyalkarylamine. 
     
     
       7. The porous polymer network according to  claim 1 , wherein the polyamine is represented by N(A 1 )A 2 , wherein A 1  and A 2  are each independently selected from —H, a branched or unbranched alkyl or a branched or unbranched alkylamine having 1 to 12 carbon atoms which is optionally mono- or polysubstituted by —OH or —NH 2 , and wherein one or more non-adjacent —CH 2  groups is optionally replaced, in each case independently from another by —O—, or —N(A 3 ), wherein A 3  is —H, a branched or unbranched alkyl or a branched or unbranched alkylamine having 1 to 12 carbon atoms, with the proviso that at least one of A 1  and A 2  is not hydrogen. 
     
     
       8. The porous polymer network according to  claim 7 , wherein N(A 1 )A 2  is selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
     
     
       9. The porous polymer network according to  claim 8 , wherein N(A 1 )A 2  is 
       
         
           
           
               
               
           
         
       
     
     
       10. The porous polymer network according to  claim 1 , wherein the proportion of amine per gram of the porous polymer network is in the range of 1 to 1000 mmol. 
     
     
       11. A method of preparing a porous polymer network, comprising:
 (a) a step of homo-coupling a monomer of formula 1 
 
       
         
           
           
               
               
           
         
         in the presence of 2,2′-bipyridyl, 1,5-cycloocta-1,5-diene, a mixed solvent of DMF/THF and a compound or mixture selected from the group consisting of bis(1,5-cycloocta-1,5-diene)nickel(0), Ni(PPH 3 ) 4  and Zn/NiCl 2 /NaBr/PPH 3 , at a temperature in the range of 20 to 40° C., 
         wherein T is —C, —Si, —Ge, —Sn, —P, —B, —N, —C 10 H 16 , —NO 2 , —CHO, —OH, —OCH 3  or —OCH 2 CH 3 , 
         R is —F, —Cl, —Br, —I, an alkenyl group or an alkynyl group, 
         R 1  to R 16  are each independently selected from —H, —F, —Cl, —Br, —I, —OH, —NH 2  and an alkyl group; and 
         (b) a step of functionalizing the product obtained in step (a) with CH 2 Q wherein Q is a polyamine. 
       
     
     
       12. The method according to  claim 11 , wherein T is selected from the group consisting of —C, —Si, —Ge and —C 10 H 16 . 
     
     
       13. The method according to  claim 11 , wherein T is —C or —Si. 
     
     
       14. The method according to  claim 11 , wherein the polyamine is represented by formula N(B 1 )B 2 , wherein B 1  and B 2  are each independently selected from —H, a saturated or unsaturated polyalkylamine and a saturated or unsaturated polyalkarylamine. 
     
     
       15. The method according to  claim 11 , wherein the polyamine is represented by formula N(B 1 )B 2 , wherein B 1 , and B 2  are each independently selected from —H, a branched or unbranched alkyl or a branched or unbranched alkylamine having 1 to 12 carbon atoms which is optionally mono- or polysubstituted by —OH or —NH 2 , and wherein one or more non-adjacent —CH 2  groups is optionally replaced, in each case independently from another by —O—, or —N(A 3 ), wherein A 3  is —H, a branched or unbranched alkyl or a branched or unbranched alkylamine having 1 to 12 carbon atoms, with the proviso that at least one of B 1  and B 2  is not hydrogen. 
     
     
       16. The method according to  claim 11 , wherein the ratio of THF to DMF is in the range of 1:10 to 10:1. 
     
     
       17. A method of storing a gas comprising incorporating a gas into the porous polymer network according to  claim 1 . 
     
     
       18. The method of storing a gas according to  claim 17 , wherein the gas is CH 4 . 
     
     
       19. A method of separating a gas from a gaseous mixture, comprising a step of contacting the gaseous mixture with a porous polymer network according to  claim 1  such that a selected gas is incorporated into the porous polymer network and is thereby separated from the gaseous mixture. 
     
     
       20. The method according to  claim 19 , wherein the gaseous mixture comprises CO 2  and N 2 .